Abstract [en]

Stereocontrolledp alladium(I1)-catalyzed1 ,4-chloro-and 1,4-acetoxylactonizationso f conjugated cyclic dienes have been developed to give stereodefined fused lactones. The stereochemistry of the 1,4- acetoxylactonization was controlled by the ligand on the metal catalyst, and in this way either a cisor truns-acetoxylactonization was obtained. This dual stereoselectivity is explained by a stereocontrolled acetate attack (trans or cis, respectively) on the allyl group in the catalytic (π-allyl)- palladium intermediate. To further strengthen the mechanism the intermediate (π-ally1)palladium complex was isolated and fully characterized. A stereospecific synthesis of cis- and truns-2-[6- (benzyloxy)-2,4-heptadien-l-yllacetic a cid (cis- and truns-9) followed by stereoselective Pd(I1)- catalyzed chloro- and acetoxylactonization in acetonelacetic acid resulted in highly functionalized fused lactones with control of the relative stereochemistry at four different carbons.